Achieving a Thermodynamic Self‐Regulation Dynamic Adsorption Mechanism for Ammonia Synthesis through Selective Orbital Coupling

With the continuous pursuing on the improvement of catalytic activity, a catalyst performed exceeding catalytic volcano plots is desired, while it is impeded by the adsorption‐energy scaling relations of reaction intermediates. Numerous efforts have been focused on optimizing the initial and final intermediates to circumvent the scaling relations for an improved performance. For a step forward, simultaneously optimizing all intermediates is essential to explore the theoretical maximum of catalytic activity. Herein, we proposed a dynamic adsorption mechanism (DAM) to independently regulate the adsorption configurations of all intermediates of electrochemical nitrogen reduction reaction (NRR). To demonstrate the DAM, a multi‐site NbNi3 intermetallic is developed, which enables suitable adsorption energies of different intermediates via modulating orbital coupling mechanisms. As a result, NbNi3 achieves an ultra‐low limiting potential of NRR of −0.11 V vs. reversible hydrogen electrode (RHE). Strikingly, the theoretical result is confirmed by a proof‐of‐concept experiment, wherein the nanoporous NbNi3 electrode exhibits a remarkable NH3 yield rate of 25.89 μg h−1 cm−2 with the Faradic efficiency of 33.15% at −0.25 V vs. RHE. Overall, this work brings out a new strategy to avoid the scaling relations, and opens up a promising avenue toward high‐efficiency NRR catalysts.